Production of clean hydrogen energy from water splitting is vital for the future fuel industry, and nanocomposites have emerged as effective catalysts for the hydrogen evolution reaction (HER). In this study, Ru-CoO@SNG nanocomposites are prepared by controlled pyrolysis where Ru-CoO heterostructured nanoparticles are supported on nitrogen and sulfur codoped graphene oxide nanosheets. With a large surface area, the obtained composites exhibit a remarkable electrocatalytic activity toward HER in 1.0 M KOH with an overpotential of only −90 mV to reach the current density of 10 mA cm−2 , in comparison to −60 mV for commercial Pt/C benchmark, along with high stability. Mechanistically, codoping of sulfur and nitrogen facilitates the dispersion of the nanoparticles, and the formation of Ru-CoO heterostructures increases the active site density, reduces the electron-transfer kinetics and boosts the catalytic performance. Results from this study highlight the unique potential of structural engineering in enhancing the electrocatalytic performance of heterostructured nanocomposites.
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Hydrogen evolution reaction catalyzed by ruthenium ion-complexed graphitic carbon nitride nanosheets
The development of cost-effective, high-performance electrocatalysts for hydrogen evolution reaction (HER) is urgently needed. In the present study, a new type of HER catalyst was developed where ruthenium ions were embedded into the molecular skeletons of graphitic carbon nitride (C 3 N 4 ) nanosheets of 2.0 ± 0.4 nm in thickness by refluxing C 3 N 4 and RuCl 3 in water. This took advantage of the strong affinity of ruthenium ions to pyridinic nitrogen of the tri- s -triazine units of C 3 N 4 . The formation of C 3 N 4 –Ru nanocomposites was confirmed by optical and X-ray photoelectron spectroscopic measurements, which suggested charge transfer from the C 3 N 4 scaffold to the ruthenium centers. Significantly, the hybrid materials were readily dispersible in water and exhibited apparent electrocatalytic activity towards HER in acid and their activity increased with the loading of ruthenium metal centers in the C 3 N 4 matrix. Within the present experimental context, the sample saturated with ruthenium ion complexation at a ruthenium to pyridinic nitrogen atomic ratio of ca. 1 : 2 displayed the best performance, with an overpotential of only 140 mV to achieve the current density of 10 mA cm −2 , a low Tafel slope of 57 mV dec −1 , and a large exchange current density of 0.072 mA cm −2 . The activity was markedly lower when C 3 N 4 was embedded with other metal ions such as Fe 3+ , Co 3+ , Ni 3+ and Cu 2+ . This suggests minimal contributions from the C 3 N 4 nanosheets to the HER activity, and the activity was most likely due to the formation of Ru–N moieties where the synergistic interactions between the carbon nitride and ruthenium metal centers facilitated the adsorption of hydrogen. This was strongly supported by results from density functional theory calculations.
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- Award ID(s):
- 1710408
- NSF-PAR ID:
- 10065709
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 5
- Issue:
- 34
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 18261 to 18269
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Sustainable hydrogen gas production is critical for future fuel infrastructure. Here, a series of phosphorous-doped carbon nitride materials were synthesized by thermal annealing of urea and ammonium hexafluorophosphate, and platinum was atomically dispersed within the structural scaffold by thermal refluxing with Zeise's salt forming Pt–N/P/Cl coordination interactions, as manifested in X-ray photoelectron and absorption spectroscopic measurements. The resulting materials were found to exhibit markedly enhanced electrocatalytic activity towards the hydrogen evolution reaction (HER) in acidic media, as compared to the P-free counterpart. This was accounted for by P doping that led to a significantly improved charge carrier density within C 3 N 4 , and the sample with the optimal P content showed an overpotential of only −22 mV to reach the current density of 10 mA cm −2 , lower than that of commercial Pt/C (−26 mV), and a mass activity (7.1 mA μg−1Pt at −70 mV vs. reversible hydrogen electrode) nearly triple that of the latter. Results from the present study highlight the significance of P doping in the manipulation of the electronic structures of metal/carbon nitride nanocomposites for high-performance HER electrocatalysis.more » « less
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Abstract Ruthenium has been hailed as a competitive alternative for platinum toward hydrogen evolution reaction (HER), a critical process in electrochemical water splitting. In this study, we successfully prepare metallic Ru nanoparticles supported on carbon paper by utilizing a novel magnetic induction heating (MIH) method. The samples are obtained within seconds, featuring a Cl‐enriched surface that is unattainable via conventional thermal annealing. The best sample within the series shows a remarkable HER activity in both acidic and alkaline media with an overpotential of only ‐23 and ‐12 mV to reach the current density of 10 mA/cm2, highly comparable to that of the Pt/C benchmark. Theoretical studies based on density functional theory show that the excellent electrocatalytic activity is accounted by the surface metal‐Cl species that facilitate charge transfer and downshift the d‐band center. Results from this study highlight the unique advantages of MIH in rapid sample preparation, where residual anion ligands play a critical role in manipulating the electronic properties of the metal surfaces and the eventual electrocatalytic activity.
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Abstract 2D early transition metal carbide and nitride MXenes have intriguing properties for electrochemical energy storage and electrocatalysis. These properties can be manipulated by modifying the basal plane chemistry. Here, mixed transition metal nitride MXenes, M‐Ti4N3Tx(M = V, Cr, Mo, or Mn; Tx= O and/or OH), are developed by modifying pristine exfoliated Ti4N3TxMXene with V, Cr, Mo, and Mn salts using a simple solution‐based method. The resulting mixed transition metal nitride MXenes contain 6–51% metal loading (cf. Ti) that exhibit rich electrochemistry including highly tunable hydrogen evolution reaction (HER) electrocatalytic activity in a 0.5
m H2SO4electrolyte as follows: V‐Ti4N3Tx> Cr‐Ti4N3Tx> Mo‐Ti4N3Tx> Mn‐Ti4N3Tx> pristine Ti4N3Txwith overpotentials as low as 330 mV at −10 mA cm−2with a charge‐transfer resistance of 70 Ω. Scanning electrochemical microscopy (SECM) reveals the electrochemical activity of individual MXene flakes. The SECM data corroborate the bulk HER activity trend for M‐Ti4N3Txas well as provide the first experimental evidence that HER results from catalysis on the MXene basal plane. These electrocatalytic results demonstrate a new pathway to tune the electrochemical properties of MXenes for water splitting and related electrochemical applications. -
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Abstract Nickel sulfide (Ni3S2) is a promising hydrogen evolution reaction (HER) catalyst by virtue of its metallic electrical conductivity and excellent stability in alkaline medium. However, the reported catalytic activities for Ni3S2are still relatively low. Herein, an effective strategy to boost the H adsorption capability and HER performance of Ni3S2through nitrogen (N) doping is demonstrated. N‐doped Ni3S2nanosheets achieve a fairly low overpotential of 155 mV at 10 mA cm−2and an excellent exchange current density of 0.42 mA cm−2in 1.0
m KOH electrolyte. The mass activity of 16.9 mA mg−1and turnover frequency of 2.4 s−1obtained at 155 mV are significantly higher than the values reported for other Ni3S2‐based HER catalysts, and comparable to the performance of best HER catalysts in alkaline medium. These experimental data together with theoretical analysis suggest that the outstanding catalytic activity of N‐doped Ni3S2is due to the enriched active sites with favorable H adsorption free energy. The activity in the Ni3S2is highly correlated with the coordination number of the surface S atoms and the charge depletion of neighbor Ni atoms. These new findings provide important guidance for future experimental design and synthesis of optimal HER catalysts.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c7ta03826g
